CN108911988B - Green synthesis method of 2-hydroxy-3-nitroacetophenone - Google Patents
Green synthesis method of 2-hydroxy-3-nitroacetophenone Download PDFInfo
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- CN108911988B CN108911988B CN201810612804.5A CN201810612804A CN108911988B CN 108911988 B CN108911988 B CN 108911988B CN 201810612804 A CN201810612804 A CN 201810612804A CN 108911988 B CN108911988 B CN 108911988B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/08—Copper compounds
Abstract
A green synthesis method of 2-hydroxy-3-nitroacetophenone is characterized by comprising the following synthesis reaction steps: using carboxylic acid as a solvent, adding a metal salt catalyst into m-nitroacetophenone to perform catalytic oxidation reaction, and performing directional hydroxylation on the m-nitroacetophenone to obtain 2-hydroxy-3-nitroacetophenone, wherein the reaction equation is as follows:
Description
Technical Field
The invention relates to the technical field of medical intermediates, in particular to a green synthesis method of 2-hydroxy-3-nitroacetophenone.
Background
For more than a decade, transition and noble metal catalyzed targeting activates SPs2Hydroxylation of carbon-hydrogen bonds has been reported:
the group of Reinaud topics reported in 1990 copper catalyzed ortho hydroxylation of aromatic hydrocarbons (ref: J. chem. Soc. chem. commun.1990, 566), the reaction scheme is as follows:
in 2006 CHEN et al reported that pyridine-directed copper catalyzed hydroxylation of 2-phenylpyridine (ref: J.Am.chem.Soc, 2006, 128, 6790) by the following reaction scheme:
the 2012 Ackermann topic group reported that Ru (II) catalyzes the keto-oriented benzene ring ortho hydroxylation reaction (ref: org. Lett.2012, 14, 6206), the reaction scheme is as follows:
the role of the directing group plays a decisive role in the three reactions described above.
2-hydroxy-3-nitroacetophenone is an important medical intermediate, can be used for synthesizing pranlukast which is an anti-allergic and anti-asthma drug, at present, 2-hydroxy-3-nitroacetophenone is mainly obtained by nitration and separation of o-hydroxyacetophenone, and the yield is lower than 40%.
Therefore, the emergence of a green synthesis method of 2-hydroxy-3-nitroacetophenone is urgently needed, the green synthesis reaction skillfully utilizes the ketone carbonyl and the nitro in m-nitroacetophenone molecules as bidentate guiding groups, the carboxylic acid is used as a solvent, the m-nitroacetophenone is added with a metal salt catalyst to carry out catalytic oxidation reaction to ensure that the m-nitroacetophenone is subjected to directional hydroxylation, and the yield of the 2-hydroxy-3-nitroacetophenone obtained by the synthesis reaction is remarkably improved, so that the method is environment-friendly, and the production cost is saved.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a green synthesis method of 2-hydroxy-3-nitroacetophenone, the green synthesis reaction ingeniously utilizes a ketone carbonyl group and a nitro group in a m-nitroacetophenone molecule as bidentate guiding groups, the m-nitroacetophenone is subjected to a catalytic oxidation reaction by taking carboxylic acid as a solvent and adding a metal salt catalyst, so that the m-nitroacetophenone is subjected to directional hydroxylation, and the yield of the 2-hydroxy-3-nitroacetophenone obtained by the synthesis reaction is remarkably improved, so that the method is environment-friendly, and the production cost is saved.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a green synthesis method of 2-hydroxy-3-nitroacetophenone comprises the following synthesis reaction steps: using carboxylic acid as a solvent, adding a metal salt catalyst into m-nitroacetophenone to perform catalytic oxidation reaction, and performing directional hydroxylation on the m-nitroacetophenone to obtain 2-hydroxy-3-nitroacetophenone, wherein the reaction equation is as follows:
the green synthesis method of the 2-hydroxy-3-nitroacetophenone skillfully utilizes the ketone carbonyl and the nitro in the m-nitroacetophenone molecule as the bidentate guiding group, the carboxylic acid is used as a solvent, the m-nitroacetophenone is added with a metal salt catalyst to carry out catalytic oxidation reaction to ensure that the m-nitroacetophenone is subjected to directional hydroxylation, and the yield of the 2-hydroxy-3-nitroacetophenone obtained by the synthesis reaction is obviously improved, so that the method is environment-friendly, and the production cost is saved.
On the basis of the technical scheme, the invention can be further improved as follows:
preferably, the molar ratio of the metal salt catalyst to the m-nitroacetophenone is 1: 10-1000.
Preferably, the weight ratio of the m-nitroacetophenone to the carboxylic acid is 1: 2-5.
Preferably, the mass percentage concentration of the carboxylic acid is 49% -51%.
Preferably, the carboxylic acid is any one of acetic acid, propionic acid or butyric acid.
Preferably, the metal salt catalyst is any one of divalent copper ion acetate, divalent nickel ion acetate or divalent palladium ion acetate.
Preferably, the synthesis reaction temperature in the synthesis reaction step is 50 ℃ to 120 ℃.
Preferably, the pressure of the synthesis reaction air in the synthesis reaction step is 0.5MPa to 1 MPa.
Preferably, the synthesis reaction time in the synthesis reaction step is 5h to 10 h.
As a preferred scheme, the synthetic reaction steps further comprise the steps of sampling and detecting the residual rate of the m-nitroacetophenone after the synthetic reaction, discharging and cooling, filtering and vacuum drying at 60-70 ℃ for 5-8 h.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the reagents used in the following examples are commercially available from normal sources.
Unless otherwise indicated, 2-hydroxy-3-nitroacetophenone was quantified by Gas Chromatography (GC) and High Performance Liquid Chromatography (HPLC) in the following examples.
Gas Chromatography (GC): the temperature of an Agilent DB-1 gas chromatographic column is 60 ℃, 30 ℃ per minute and 180 ℃; then the temperature is increased to 240 ℃ by 3 ℃ per minute, and the temperature is kept for 3 minutes; the vaporization temperature is 280 ℃, and the detection temperature is 300 ℃;
high Performance Liquid Chromatography (HPLC): and (2) an ODS-3 liquid chromatography column, wherein the mobile phase comprises water, acetonitrile, triethylamine and acetic acid, and the mass ratio of the water to the acetonitrile to the triethylamine to the acetic acid is 400: 600: 0.5: 1; the wavelength is 254 nm;
a green synthesis method of 2-hydroxy-3-nitroacetophenone comprises the following synthesis reaction steps: using carboxylic acid as a solvent, adding a metal salt catalyst into m-nitroacetophenone to perform catalytic oxidation reaction, and performing directional hydroxylation on the m-nitroacetophenone to obtain 2-hydroxy-3-nitroacetophenone, wherein the reaction equation is as follows:
the green synthesis method of the 2-hydroxy-3-nitroacetophenone skillfully utilizes the ketone carbonyl and the nitro in the m-nitroacetophenone molecule as the bidentate guiding group, the carboxylic acid is used as a solvent, the m-nitroacetophenone is added with a metal salt catalyst to carry out catalytic oxidation reaction to ensure that the m-nitroacetophenone is subjected to directional hydroxylation, the yield of the 2-hydroxy-3-nitroacetophenone obtained by the synthesis reaction is obviously improved, the synthesis reaction is environment-friendly, and the production cost is saved.
On the basis of the technical scheme, the invention can be further improved as follows:
in some embodiments, the molar ratio of the metal salt catalyst to the m-nitroacetophenone is from 1:10 to 1000.
In some embodiments, the weight ratio of the m-nitroacetophenone to the carboxylic acid is from 1:2 to 5.
In some embodiments, the carboxylic acid is present at a concentration of 49% to 51% by weight.
In some embodiments, the carboxylic acid is any of acetic acid, propionic acid, or butyric acid.
In some embodiments, the metal salt catalyst is any one of divalent copper ion acetate, divalent nickel ion acetate, or divalent palladium ion acetate.
In some embodiments, the synthesis reaction temperature in the synthesis reaction step is from 50 ℃ to 120 ℃.
In some embodiments, the synthesis reaction air pressure in the synthesis reaction step is from 0.5MPa to 1 MPa.
In some embodiments, the synthesis reaction time in the synthesis reaction step is from 5h to 10 h.
In some embodiments, the step of the synthetic reaction further comprises the steps of sampling and detecting the residual rate of the m-nitroacetophenone after the synthetic reaction, discharging and cooling, filtering and vacuum drying at 60-70 ℃ for 5-8 h.
In the case of the example 1, the following examples are given,
163 g (1 mol) of m-nitroacetophenone, 20 g (0.1 mol) of copper acetate monohydrate and 326 g of 50% W/W (mass percentage concentration) acetic acid are added into a pressure kettle, the pressure kettle is pressurized to 0.8MPa by air, the temperature is increased to 100-105 ℃, the stirring reaction is carried out for 10 hours, the m-nitroacetophenone residual rate is 1.55% by sampling detection (obtained by detecting through High Performance Liquid Chromatography (HPLC) or Gas Chromatography (GC)), the temperature is reduced to 90 ℃, the hot material liquid is discharged, the temperature of the material liquid is reduced to 5 ℃, then the material liquid is filtered, and finally, the vacuum drying is carried out for 5 hours at the temperature of 60-70 ℃ to obtain 160 g of 2-hydroxy-3-nitroacetophenone, the yield is 89%, and the content is 98.2% (obtained by detecting through the High Performance Liquid Chromatography (HPLC) or the Gas Chromatography (GC)).
In the case of the example 2, the following examples are given,
163 g (1 mol) of m-nitroacetophenone, 12.44 g (0.05 mol) of nickel acetate tetrahydrate and 326 g of 49% W/W (mass percentage concentration) propionic acid are added into a pressure kettle, the pressure kettle is pressurized to 1MPa by air, the temperature is increased to 100-105 ℃, the stirring reaction is carried out for 10 hours, the m-nitroacetophenone residual rate is 1.1% by sampling detection (obtained by detecting through High Performance Liquid Chromatography (HPLC) or Gas Chromatography (GC)), the temperature is reduced to 90 ℃, the hot material liquid is discharged, the temperature of the material liquid is reduced to 0 ℃, then the material liquid is filtered, and finally, the vacuum drying is carried out at 60-70 ℃ for 8 hours, so that 165 g of 2-hydroxy-3-nitroacetophenone is obtained, the yield is 92%, and the content is 98.5% (obtained by detecting through the High Performance Liquid Chromatography (HPLC) or the Gas Chromatography (GC)).
In the case of the example 3, the following examples are given,
163 g (1 mol) of m-nitroacetophenone, 1.12 g (0.005 mol) of palladium acetate and 326 g of 51% W/W (mass percentage concentration) butyric acid are added into a pressure kettle, the pressure kettle is pressurized to 0.5MPa by air, the temperature is increased to 50-55 ℃, the stirring reaction is carried out for 5h, the m-nitroacetophenone residue rate is 2.5% by sampling detection (obtained by detecting through High Performance Liquid Chromatography (HPLC) or Gas Chromatography (GC)), the discharging temperature is reduced to 5 ℃, then, the filtering is carried out, and finally, the vacuum drying is carried out for 7h at the temperature of 60-70 ℃ to obtain 156 g of 2-hydroxy-3-nitroacetophenone, the yield is 87%, and the content is 97.8% (obtained by detecting through the High Performance Liquid Chromatography (HPLC) or the Gas Chromatography (GC)).
In the case of the example 4, the following examples are given,
163 g (1 mol) of m-nitroacetophenone, 0.224 g (0.001 mol) of palladium acetate and 326 g of 50% W/W (mass percentage concentration) acetic acid are added into a pressure kettle, the pressure kettle is pressurized to 1.0MPa by air, the temperature is raised to 70-75 ℃, the stirring reaction is carried out for 8h, the m-nitroacetophenone residue rate is 1.5% by sampling detection (obtained by detecting through High Performance Liquid Chromatography (HPLC) or Gas Chromatography (GC)), the discharging temperature is reduced to 0 ℃, then, the filtering is carried out, and finally, the vacuum drying is carried out for 5h at the temperature of 60-70 ℃ to obtain 166 g of 2-hydroxy-3-nitroacetophenone, the yield is 92.7%, and the content is 98.3% (obtained by detecting through the High Performance Liquid Chromatography (HPLC) or the Gas Chromatography (GC)).
In the case of the example 5, the following examples were conducted,
163 g (1 mol) of m-nitroacetophenone, 2 g (0.01 mol) of copper acetate monohydrate and 326 g of 50% W/W (mass percentage concentration) acetic acid are added into a pressure kettle, the pressure kettle is pressurized to 1.0MPa by air, the temperature is increased to 115-120 ℃, the stirring reaction is carried out for 10 hours, the m-nitroacetophenone residual rate is 2.55% by sampling detection (obtained by detecting through High Performance Liquid Chromatography (HPLC) or Gas Chromatography (GC)), the temperature is reduced to 90 ℃, the material liquid is discharged when the material liquid is hot, then the temperature of the material liquid is reduced to 5 ℃, then the material liquid is filtered, and finally the vacuum drying is carried out for 5 hours at the temperature of 60-70 ℃, so that 158 g of 2-hydroxy-3-nitroacetophenone is obtained, the yield is 87.7%, and the content is 98.1% (obtained by detecting through the High Performance Liquid Chromatography (HPLC) or the gas chromatography.
In the case of the example 6, it is shown,
163 g (1 mol) of m-nitroacetophenone, 1.24 g (0.005 mol) of nickel acetate tetrahydrate and 326 g of 50% W/W (mass percentage concentration) propionic acid are added into a pressure kettle, the pressure kettle is pressurized to 1.0MPa by air, the temperature is raised to 90-95 ℃, the stirring reaction is carried out for 10 hours, the residual rate of the m-nitroacetophenone is 2.6% by sampling detection (obtained by detecting through High Performance Liquid Chromatography (HPLC) or Gas Chromatography (GC)), the temperature is reduced to 90 ℃, the material liquid is discharged when the material liquid is hot, the temperature of the material liquid is reduced to 0 ℃, then the material liquid is filtered, and finally the vacuum drying is carried out at 60-70 ℃ for 5 hours, so that 161 g of 2-hydroxy-3-nitroacetophenone is obtained, the yield is 89.9%, and the content is 98.0% (obtained by detecting through the High Performance Liquid Chromatography (HPLC) or the gas.
The green synthesis method of the 2-hydroxy-3-nitroacetophenone skillfully utilizes the ketone carbonyl and the nitro in the m-nitroacetophenone molecule as the bidentate guiding group, the carboxylic acid is used as a solvent, the m-nitroacetophenone is added with a metal salt catalyst to carry out catalytic oxidation reaction to ensure that the m-nitroacetophenone is subjected to directional hydroxylation, the yield of the 2-hydroxy-3-nitroacetophenone obtained by the synthesis reaction is obviously improved, the synthesis reaction is environment-friendly, and the production cost is saved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (9)
1. A green synthesis method of 2-hydroxy-3-nitroacetophenone is characterized by comprising the following synthesis reaction steps: using carboxylic acid as a solvent, adding a metal salt catalyst into m-nitroacetophenone to perform catalytic oxidation reaction, and performing directional hydroxylation on the m-nitroacetophenone to obtain 2-hydroxy-3-nitroacetophenone, wherein the reaction equation is as follows:
the metal salt catalyst is any one of divalent copper ion acetate, divalent nickel ion acetate or divalent palladium ion acetate.
2. The green synthesis method of 2-hydroxy-3-nitroacetophenone according to claim 1, wherein the molar ratio of the metal salt catalyst to the m-nitroacetophenone is 1: 10-1000.
3. The green synthesis method of 2-hydroxy-3-nitroacetophenone according to claim 1, wherein the weight ratio of the m-nitroacetophenone to the carboxylic acid is 1: 2-5.
4. The green synthesis method of 2-hydroxy-3-nitroacetophenone according to claim 3, wherein the mass percent concentration of the carboxylic acid is 49 to 51%.
5. The green synthesis method of 2-hydroxy-3-nitroacetophenone according to claim 4, wherein the carboxylic acid is any one of acetic acid, propionic acid or butyric acid.
6. The green synthesis method of 2-hydroxy-3-nitroacetophenone according to claim 1, wherein the synthesis reaction temperature in the synthesis reaction step is from 50 ℃ to 120 ℃.
7. The green synthesis method of 2-hydroxy-3-nitroacetophenone according to claim 1, wherein the pressure of the synthesis reaction air in the synthesis reaction step is from 0.5MPa to 1 MPa.
8. The green synthesis method of 2-hydroxy-3-nitroacetophenone according to claim 1, wherein the synthesis reaction time in the synthesis reaction step is 5 to 10 hours.
9. The green synthesis method of 2-hydroxy-3-nitroacetophenone according to claim 1, wherein the synthesis reaction step further comprises the steps of sampling after the synthesis reaction to detect the residual rate of m-nitroacetophenone, discharging, cooling, filtering and vacuum drying at 60-70 ℃ for 5-8 h.
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